CN110387559A - A kind of electro-catalysis produces the preparation method and its product and application of oxygen thin-film electrode material - Google Patents
A kind of electro-catalysis produces the preparation method and its product and application of oxygen thin-film electrode material Download PDFInfo
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Abstract
The invention belongs to the technical fields of electrode material preparation, and in particular to a kind of electro-catalysis produces the preparation method and its product and application of oxygen thin-film electrode material.The present invention grows Prussian blue similar object film using liquid phase epitaxial process in nickel foam, and then calcining carries out oxidation processes and obtains sull in air.This method have aggregate velocity is fast, preparation efficiency is high, film size is controllable, film thickness is controllable, environmentally friendly, at low cost and simple operation and other advantages, for its on a large scale prepare provide a kind of convenient and fast method.Electro-catalysis prepared by the present invention produces oxygen thin-film electrode material and is used directly for the working electrode that electro-catalysis produces oxygen, electric conductivity is preferable, furthermore it further improves and produces oxygen field in electro-catalysis in the prior art, glass-carbon electrode is poor as collector performance, electrode material surface active material poor adhesive force, it is easy to fall off the problems such as, make its electro-catalysis produce the field oxygen (OER) have a good application prospect.
Description
Technical field
The invention belongs to the technical fields of electrode material preparation, and in particular to a kind of electro-catalysis produces oxygen thin-film electrode material
Preparation method and its product and application.
Background technique
Economic fast development is increasing for the demand of the energy, and the reserves of conventional fossil fuel are limited, and largely disappear
Environmental problem caused by consumption fossil fuel is got worse, therefore develops cleaning, and efficient energy and material is particularly important.Hydrogen
A kind of rich reserves, clean and effective, the energy and material of sustainable use, electrolysis water prepare hydrogen be one of hydrogen it is important come
Source, and the anode half-reaction of electrolysis water produce oxygen reaction (OER) and generally require to overcome higher overpotential, consume higher energy,
Therefore it develops efficiently, inexpensively, the OER catalyst of high stability is one of the hot issue of current scientist's concern.
Studies have shown that metal oxide containing precious metals, if ruthenic oxide and iridium dioxide are efficient OER catalyst, but because of it
Expensive, reserves are limited to constrain its practical application.The transition metal oxide of current some powders, sulfide, phosphide
It is widely studied, but most of research is all based on to be supported on and carry out on glass-carbon electrode, is not met by practical application
It is required that.
Therefore, economical at present there is an urgent need to a kind of simple, the electro-catalysis that can be prepared on a large scale produces the preparation side of oxygen electrode
Method, so that the electrode material of preparation had not only had lower cost but also the production oxygen half that can be applied to be catalyzed in practical electrolysis water is anti-
It answers.
Summary of the invention
The purpose of the present invention is intended on the one hand reduce the cost that preparation electro-catalysis produces oxygen material, on the other hand provides a kind of high
Effect and stable oxide film electrode and its preparation method and application.The present invention will be Prussian blue using liquid phase epitaxial process
Analog (Prussian Blue Analogues, referred to as " PBAs ") is grown in nickel foam, then carries out oxygen using high-temperature calcination
The method for changing processing, is transformed into metal oxide for Prussian blue similar object therein, the oxide film material thus prepared
Electrode is used directly for the working electrode that electro-catalysis produces oxygen.This method can prepare the PBAs thin film precursor of even compact,
The sull formed after Overheating Treatment still is able to be attached in foam nickel base, and there is the efficient oxygen that produces to react
(OER) catalytic performance.
The technical solution adopted by the invention is as follows:
A kind of electro-catalysis produces the preparation method of oxygen thin-film electrode material, comprising:
1) Prussian blue similar object (PBAs) film is grown in nickel foam using liquid phase epitaxial process；
2) material at high temperature obtained in step 1) is calcined, obtains the electro-catalysis and produces oxygen thin-film electrode material, the material
Including nickel foam and the metal-oxide film being attached in nickel foam.
According to the present invention, the main component of the metal-oxide film is MM '2O4, wherein M be selected from divalent metal from
Son, M ' are selected from trivalent metal ion.
For example, the M is selected from Co2+、Fe2+、Zn2+、Mn2+、Ni2+、Cd2+Or Cu2+；M ' is selected from Co3+、Al3+、Fe3+、Ni3+、
Mn3+、Cr3+、Ln3+Deng, wherein Ln3+For rare earth ion, it is selected from La3+、Ce3+、Pr3+、Nd3+、Pm3+、Sm3+、Eu3+、Gd3+、Tb3+、
Dy3+、Ho3+、Er3+、Tm3+、Yb3+、Lu3+、Y3+Or Sc3+。
According to the present invention, the M can be identical or not identical with the metal of M '.
Specifically, the main component of the metal-oxide film is CoFe2O4、ZnFe2O4、MnFe2O4、FeMn2O4、
NiFe2O4、CdFe2O4、CuFe2O4、FeCo2O4、Co3O4、ZnCo2O4、MnCo2O4、NiCo2O4、CdCo2O4、CuCo2O4、
MnAl2O4、FeAl2O4、CoAl2O4、NiAl2O4、CuAl2O4、ZnAl2O4、ZnNi2O4、CoNi2O4、MnNi2O4、CoCr2O4、
NiCr2O4、FeCr2O4、FeLn2O4、CoLn2O4、NiLn2O4, wherein Ln is rare earth element, selected from La, Ce, Pr, Nd, Pm, Sm,
Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y or Sc.
According to the present invention, the PBAs is the compound and K with the metal ion containing M3[M’(CN)6], or the metal ion containing M '
Compound and K4[M(CN)6] formed the complex with certain space structure.
Preferably, the compound of the metal ion containing M is selected from M (CH3COO)2、MSO4、M(NO3)2Or MCl2Deng.
Preferably, the compound of the metal ion Han M ' is selected from M ' (CH3COO)3、M’2(SO4)3、M’(NO3)3Or M ' Cl3
Deng.
According to the present invention, the PBAs is preferably the compound and K of the metal ion containing M3[M’(CN)6] formed have one
Determine the complex of space structure.
For example, the PBAs can be the reaction product of the potassium ferricyanide and cobalt acetate: Co3[Fe(CN)6]2, abbreviation PBA
(Co-Fe)。
According to the present invention, the preparation method that the electro-catalysis produces oxygen thin-film electrode material can be with specifically:
S1, prepare the metal ion containing M compound solution and K3[M’(CN)6] solution, alternatively, prepare the metal containing M '
The solution and K of the compound of ion4[M(CN)6] solution；
S2, cleaning foam nickel base；
S3, nickel foam is immersed in the metal ion containing M compound solution and K3[M’(CN)6] solution in, alternatively,
Nickel foam is immersed in the solution and K of the compound of the metal ion containing M '4[M(CN)6] solution in, pass through rheotaxial growth
The film layer of method formation PBAs；
S4, step S3 is repeated, obtains being grown in the PBAs film in nickel foam；
S5, high-temperature calcination obtain the electro-catalysis and produce oxygen thin-film electrode material.
According to the present invention, in step S1, the solvent of the solution can be water.
In step S1, the concentration of the compound of the compound or metal ion Han M ' of the metal ion containing M can in the solution
Think 2 to 10mmol/L, preferably 3mmol/L.
In step S1, K in the solution3[M’(CN)6] or K4[M(CN)6] concentration can be 2 to 10mmol/L, preferably
For 2mmol/L.
According to the present invention, in step S2, the cleaning can be with are as follows: is cleaned by ultrasonic nickel foam using dilute hydrochloric acid solution, then
It is cleaned by ultrasonic in distilled water for several times, dries.
According to the present invention, in step S3, the reaction is preferably using the method impregnated manually.
In step S3, the reaction can carry out in the device of rheotaxial growth.
In step S3, the method for PBAs film is prepared in nickel foam for example including following steps: in the metal ion containing M
Solution and K3[M’(CN)6] solution in successively impregnate nickel foam, in nickel foam formed PBAs film；Alternatively, in the metal containing M '
The solution and K of ion4[M(CN)6] solution in successively impregnate nickel foam, in nickel foam formed PBAs film.
Wherein, the solution and K of the compound of the metal ion containing M3[M’(CN)6] solution dosage can it is identical or
Difference, the dosage of the solution do not cross nickel foam preferably；Alternatively, the solution and K of the compound of the metal ion Han M '4[M
(CN)6] the dosage of solution can be identical or different, the dosage of the solution does not cross nickel foam preferably.
Wherein, the temperature of the immersion can be identical or different, is independently from each other 25-80 DEG C, such as 50-80 DEG C；
Preferably, the soaking process can carry out under water bath condition.
Wherein, the time of the immersion can be identical or different, is independently from each other 15 to 60 minutes, preferably 20 to
25 minutes.
Preferably, in the solution and K of the compound for having impregnated the metal ion containing M3[M’(CN)6] solution after, alternatively, In
The solution and K of the compound of the metal ion Han M ' are impregnated4[M(CN)6] solution after, further include it is respectively stood so that its
The step of sufficiently reacting.The time of the standing can be 3-5 minutes.
It is further preferred that further including removing the step of remaining reaction raw materials using distilled water after standing reaction.
Preferably, the successively immersion sequence are as follows: solution → distilled water → K of the compound of the metal ion containing M3[M’
(CN)6] solution → distilled water, alternatively, solution → distilled water → K of the compound of the metal ion Han M '4[M(CN)6] solution
→ distilled water.
According to the present invention, in step S4, the duplicate number is 10 times or more, such as 15 times.
According to the present invention, in step S5, the reaction can carry out in Muffle furnace.
In step S5, the temperature of the calcining can be 200-500 DEG C, such as 250 DEG C, 350 DEG C or 450 DEG C.
In step S5, the time of the calcining can be 1-5 hours, preferably 2 hours.
In step S5, the calcining can carry out in air.
According to the present invention, the preparation method that the electro-catalysis produces oxygen thin-film electrode material can be with specifically:
The solution of S1, the solution for preparing cobalt acetate and the potassium ferricyanide；
S2, cleaning foam nickel base；
S3, nickel foam is immersed in the solution of cobalt acetate and the solution of the potassium ferricyanide, passes through liquid phase epitaxial process shape
At the film layer of PBAs；
S4, step S3 is repeated, obtains being grown in the PBAs film in nickel foam；
S5, high-temperature calcination obtain electro-catalysis and produce oxygen thin-film electrode material.
According to the present invention, the method for PBAs film is prepared in nickel foam for example including following steps: by the molten of cobalt acetate
The solution of liquid and the potassium ferricyanide successively impregnates nickel foam, and PBA (Co-Fe) film: PBA (Co-Fe)/NF is formed in nickel foam.
Preferably, the successively immersion sequence are as follows: cobalt acetate solution → distilled water → potassium ferricyanide solution → distilled water.
According to the present invention, the thickness of PBAs film can be controlled by controlling the number of repetitive operation as described above, reached
Need to prepare different PBAs film thicknesses according to different uses.
According to the present invention, the electrode material of different area in order to obtain selects the bubble of different area according to the usage requirement
Foam nickel.
The present invention also provides following scheme:
A kind of electro-catalysis production oxygen thin-film electrode material, passes through the preparation side that above-mentioned electro-catalysis produces oxygen thin-film electrode material
Method is prepared, which includes nickel foam and the metal-oxide film that is attached in nickel foam.
Preferably, the main component of the metal-oxide film is MM '2O4, wherein M is selected from bivalent metal ion, M '
Selected from trivalent metal ion.
For example, the M is selected from Co2+、Fe2+、Zn2+、Mn2+、Ni2+、Cd2+Or Cu2+；M ' is selected from Co3+、Al3+、Fe3+、Ni3+、
Mn3+、Cr3+、Ln3+Deng, wherein Ln3+For rare earth ion, it is selected from La3+、Ce3+、Pr3+、Nd3+、Pm3+、Sm3+、Eu3+、Gd3+、Tb3+、
Dy3+、Ho3+、Er3+、Tm3+、Yb3+、Lu3+、Y3+Or Sc3+。
According to the present invention, the M can be identical or not identical with the metal of M '.
Specifically, the main component of the metal-oxide film is CoFe2O4、ZnFe2O4、MnFe2O4、FeMn2O4、
NiFe2O4、CdFe2O4、CuFe2O4、FeCo2O4、Co3O4、ZnCo2O4、MnCo2O4、NiCo2O4、CdCo2O4、CuCo2O4、
MnAl2O4、FeAl2O4、CoAl2O4、NiAl2O4、CuAl2O4、ZnAl2O4、ZnNi2O4、CoNi2O4、MnNi2O4、CoCr2O4、
NiCr2O4、FeCr2O4、FeLn2O4、CoLn2O4、NiLn2O4, wherein Ln is rare earth element, selected from La, Ce, Pr, Nd, Pm, Sm,
Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y or Sc.
The present invention also provides the applications that the electro-catalysis produces oxygen thin-film electrode material, are used as working electrode, preferably electric
The anode working electrode of Xie Shui, for OER catalysis reaction.
In the preparation process in accordance with the present invention, the sull prepared by high-temperature calcination method can be used as electrode material
It is directly used in OER catalysis reaction.As it can be seen that the membrane material that the method for the present invention is prepared be by active material and collector effectively
It is combined together, can directly be used as the working electrode of OER catalysis reaction.
Beneficial effects of the present invention
The present invention provides a kind of preparation methods that oxygen performance thin-film material is produced with electro-catalysis, use liquid phase epitaxy first
Growth method grows PBAs film in foam nickel surface, such as using cobalt acetate, the potassium ferricyanide as raw material, using immersion method successively
It is assembled in layer, to be prepared into the nickel foam embedded with PBAs film.This method can during the preparation process accurately
The thickness and area of PBAs film are controlled, and preparation efficiency is high.And PBAs film can be controlled by the number of control operation
Thickness.The thickness of PBAs film can control the amount of calcining back loading substance, after the homogeneity of PBAs film can make calcining
Load substance more uniform be attached in foam nickel base.
The present invention would be embedded with the nickel foam calcining of PBAs film using the method for high-temperature calcination, obtain containing metal oxide
The electro-catalysis of film produces Oxygen Electrode Material.This method is easy to operate, high-efficient, and aggregate velocity is fast, environmentally protective, at low cost.It can
See, the present invention provides a kind of extensive and convenient and fast preparation methods.
It is preferable that electro-catalysis prepared by the present invention produces oxygen thin-film electrode material electric conductivity, convenient for the diffusion and transmission of electronics, this
It further improves outside and produces oxygen field in electro-catalysis in the prior art, glass-carbon electrode is poor as collector performance, and electrode material surface is living
Property substance poor adhesive force, it is easy to fall off the problems such as, provide for it in the application that electro-catalysis produces oxygen and other electrochemical fields wide
Prospect.
Detailed description of the invention
Fig. 1 is that the electro-catalysis prepared in embodiment 1 produces the powder diagram of oxygen thin-film electrode material (including experiment
Value, theoretical value and base foam nickel).
Fig. 2 is that the electro-catalysis prepared in embodiment 1 produces the pictorial diagram of oxygen thin-film electrode material.
Fig. 3 is the SEM figure that the electro-catalysis prepared in embodiment 1 produces oxygen thin-film electrode material.
Fig. 4 is that the electro-catalysis prepared in embodiment 1 produces LSV of the oxygen thin-film electrode material in 1.0mol/L KOH electrolyte
Curve.
Fig. 5 is that the electro-catalysis prepared in embodiment 1 produces oxygen thin-film electrode material in current density about 10mA/cm2When it is steady
Qualitative test.
Specific embodiment
The present invention provides one kind to grow PBAs film in nickel foam, and further high-temperature calcination is prepared with OER
The method of the oxide film electrode material of catalytic performance.PBAs is specially grown in nickel foam using liquid phase epitaxial process
Film, then calcining carries out oxidation processes, obtains the oxide film electrode material with OER catalytic performance.The present invention uses
Two reactants are configured to a certain proportion of solution, are preferably for example configured to aqueous solution, then lead to by liquid phase epitaxial process
It crosses the method impregnated manually and assembles PBAs film in layer, then obtained by the method for high-temperature calcination with OER catalytic performance
Oxide film electrode material.
During the preparation process, in order to enable PBAs film preferably to grow, the present invention has also carried out nickel foam sour clear
It washes, so that the preparation for film provides good growth templates.It according to the present invention, will after being cleaned and dried to nickel foam
It is placed in the device of rheotaxial growth.Material solution is impregnated clearly according to certain sequence using the method being manually injected into
Nickel foam after washing, and the time for controlling reaction carries out epitaxial growth in nickel foam.
The concentration distribution control of material solution within the above range, is mainly considered reaction speed and control by the present invention
The factors such as surface topography can achieve the effect that thickness is controllable and surface is smooth in above-mentioned numberical range.
Technical solution of the present invention is described in detail below by way of illustrative specific embodiment.But it should not be by these
Embodiment is construed to limiting the scope of the invention.All technologies realized based on above content of the present invention are encompassed by this
Invention is intended in the range of protection.
Unless otherwise indicated, raw material and reagent used in embodiment are commercial product, or can pass through known formula
Method preparation.
Embodiment 1
1) preparation of the Prussian blue similar object film of PBA (Co-Fe)/NF
Cobalt acetate and the potassium ferricyanide are weighed, each is dissolved into distilled water, being configured to concentration is respectively 3mmol/
L, each 500ml of the solution of 2mmol/L.
The cobalt acetate aqueous solution for taking configured 3mmol/L pours into brown vial, then the nickel foam cleaned up is put
Enter wherein, ampoule is put into static a period of time in 50 DEG C of water-baths, then takes out nickel foam distilled water rinse, then take and match
The potassium ferricyanide aqueous solution of the 2mmol/L set pours into brown vial, nickel foam is put into wherein, ampoule is put into 50
Static a period of time in DEG C water-bath then takes out nickel foam distilled water rinse, completes a complete manual infusion.
Wherein, the immersion amount of cobalt acetate solution is advisable with not crossing nickel foam, and soaking time is 20 minutes, is stood after immersion anti-
It is 3 minutes between seasonable, with distilled water rinse to remove remaining reaction raw materials after reaction.Potassium ferricyanide solution is impregnated later, is soaked
Bubble amount is advisable with not crossing nickel foam, and soaking time is 25 minutes, and reaction 3 minutes are stood after immersion, and distilled water rinse is used after reaction
To remove remaining reaction raw materials.Then the above raw material soaking step 15 time is repeated, PBA (Co-Fe)/NF of respective thickness is obtained
Prussian blue similar object thin-film material.
2) electro-catalysis produces the preparation of oxygen thin-film electrode material
Finally the above-mentioned nickel foam with PBA (Co-Fe) film is placed in crucible, then crucible is placed in Muffle furnace,
It is calcined 2 hours for 350 DEG C under air atmosphere, is then cooled to room temperature, obtains oxide film material.
By step 1), 2) sample obtained carries out powder diffraction characterization and scanning electron microscope characterization, as a result such as Fig. 1 and Fig. 3 institute
Show.It can be seen that Prussian blue similar object PBA (Co-Fe) film from Powder Diffraction pattern in Fig. 1 successfully to give birth in nickel foam
Long, 350 DEG C form CoFe in heat treatment 2 hours later2O4Film.As can be seen from Figure 2 the variation of base foam nickel color, by
Grey becomes black.From can be seen that the PBAs film prepared in embodiment 1 in the scanning electron microscope spectrogram of Fig. 3 through oxidation place
The sull obtained after reason is uniformly grown in nickel foam.
3) electro-catalysis produces oxygen performance test
By above-mentioned steps 2) obtained thin-film material is directly as working electrode, using Ag/AgCl as reference electrode, platinum filament
Electrode is used as to electrode, its electro-catalysis is tested in the KOH solution of 1mol/L and produces oxygen performance, as a result as shown in Figure 4.
As can be seen from Figure 4 current density is 10mA/cm in current density with the variation of voltage2When overpotential be
269mv has preferable OER performance.As can be seen from Figure 5 current density changes with time, and is about in current density
10mA/cm2When, the oxide film electrode that we prepare can continue working 20 hours, and current density is not apparent
Decaying, stability with higher.
More than, embodiments of the present invention are illustrated.But the present invention is not limited to above embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. the preparation method that a kind of electro-catalysis produces oxygen thin-film electrode material, which is characterized in that the preparation method includes following step
It is rapid:
1) Prussian blue similar object (PBAs) film is grown in nickel foam using liquid phase epitaxial process；
2) material at high temperature obtained in step 1) is calcined, obtains electro-catalysis and produce oxygen thin-film electrode material, which includes foam
Nickel and the metal-oxide film being attached in nickel foam.
2. preparation method according to claim 1, which is characterized in that the main component of the metal-oxide film is
MM’2O4, wherein M is selected from bivalent metal ion, and M ' is selected from trivalent metal ion；
The M is selected from Co2+、Fe2+、Zn2+、Mn2+、Ni2+、Cd2+Or Cu2+；The M ' is selected from Co3+、Al3+、Fe3+、Ni3+、Mn3+、
Cr3+Or Ln3+, wherein Ln3+For rare earth ion, it is selected from La3+、Ce3+、Pr3+、Nd3+、Pm3+、Sm3+、Eu3+、Gd3+、Tb3+、Dy3+、
Ho3+、Er3+、Tm3+、Yb3+、Lu3+、Y3+Or Sc3+；
Preferably, the metal phase of the M and M ' with or it is not identical.
3. preparation method according to claim 1 or 2, which is characterized in that the main component of the metal-oxide film
For CoFe2O4、ZnFe2O4、MnFe2O4、FeMn2O4、NiFe2O4、CdFe2O4、CuFe2O4、FeCo2O4、Co3O4、ZnCo2O4、
MnCo2O4、NiCo2O4、CdCo2O4、CuCo2O4、MnAl2O4、FeAl2O4、CoAl2O4、NiAl2O4、CuAl2O4、ZnAl2O4、
ZnNi2O4、CoNi2O4、MnNi2O4、CoCr2O4、NiCr2O4、FeCr2O4、FeLn2O4、CoLn2O4Or NiLn2O4, wherein Ln is
Rare earth element is selected from La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y or Sc.
4. preparation method according to claim 1-3, which is characterized in that the PBAs is with metal ion containing M
Compound and K3[M’(CN)6], or the compound and K of the metal ion Han M '4[M(CN)6] formed have certain space structure
Complex；Wherein, M, M ' there is definition as claimed in claim 2；
Preferably, the compound of the metal ion containing M is selected from M (CH3COO)2、MSO4、M(NO3)2Or MCl2；
Preferably, the compound of the metal ion Han M ' is selected from M ' (CH3COO)3、M’2(SO4)3、M’(NO3)3Or M ' Cl3；
For example, the PBAs is the reaction product of the potassium ferricyanide and cobalt acetate: Co3[Fe(CN)6]2。
5. preparation method according to claim 1-4, which is characterized in that the preparation method is that:
S1, prepare the metal ion containing M compound solution and K3[M’(CN)6] solution, alternatively, prepare the metal ion containing M '
Compound solution and K4[M(CN)6] solution；
S2, cleaning foam nickel base；
S3, nickel foam is immersed in the metal ion containing M compound solution and K3[M’(CN)6] solution in, alternatively, will bubble
Foam nickel is immersed in the solution and K of the compound of the metal ion containing M '4[M(CN)6] solution in, pass through liquid phase epitaxial process shape
At the film layer of PBAs；
S4, step S3 is repeated, obtains being grown in the PBAs film in nickel foam；
S5, high-temperature calcination obtain electro-catalysis and produce oxygen thin-film electrode material.
6. preparation method according to claim 1-5, which is characterized in that in step S1, the solvent of the solution
For water；
In step S1, in the solution concentration of the compound of the compound or metal ion Han M ' of the metal ion containing M be 2 to
10mmol/L, preferably 3mmol/L；
In step S1, K in the solution3[M’(CN)6] or K4[M(CN)6] concentration be 2 to 10mmol/L, preferably 2mmol/
L；
Preferably, in step S2, the cleaning are as follows: be cleaned by ultrasonic nickel foam using dilute hydrochloric acid solution, then surpass in distilled water
Sound cleans for several times, dries；
In step S3, the method for PBAs film is prepared in nickel foam for example including following steps: in the solution of the metal ion containing M
And K3[M’(CN)6] solution in successively impregnate nickel foam, in nickel foam formed PBAs film；Alternatively, in the metal ion containing M '
Solution and K4[M(CN)6] solution in successively impregnate nickel foam, in nickel foam formed PBAs film；
Wherein, the solution and K of the compound of the metal ion containing M3[M’(CN)6] solution dosage it is identical or different, it is described
The dosage of solution does not cross nickel foam preferably；Alternatively, the solution and K of the compound of the metal ion Han M '4[M(CN)6] it is molten
The dosage of liquid is identical or different, and the dosage of the solution does not cross nickel foam preferably；
Wherein, the temperature of the immersion is identical or different, is independently from each other 25-80 DEG C, such as 50-80 DEG C；
Wherein, the time of the immersion is identical or different, is independently from each other 15 to 60 minutes, preferably 20 to 25 minutes；
Preferably, in the solution and K of the compound for having impregnated the metal ion containing M3[M’(CN)6] solution after, alternatively, impregnating
The solution and K of the compound of the complete metal ion Han M '4[M(CN)6] solution after, further include it is respectively stood so that its sufficiently
The step of reaction；The time of the standing is 3-5 minutes；
It is further preferred that further including removing the step of remaining reaction raw materials using distilled water after standing reaction；
Preferably, the successively immersion sequence are as follows: solution → distilled water → K of the compound of the metal ion containing M3[M’(CN)6]
Solution → distilled water, alternatively, solution → distilled water → K of the compound of the metal ion Han M '4[M(CN)6] solution → distillation
Water；
In step S4, the duplicate number is 10 times or more, such as 15 times；
In step S5, the temperature of the calcining is 200-500 DEG C, such as 250 DEG C, 350 DEG C or 450 DEG C；
In step S5, the time of the calcining is 1-5 hours, preferably 2 hours.
7. preparation method according to claim 1-6, which is characterized in that the preparation method is that:
The solution of S1, the solution for preparing cobalt acetate and the potassium ferricyanide；
S2, cleaning foam nickel base；
S3, nickel foam is immersed in the solution of cobalt acetate and the solution of the potassium ferricyanide, is formed by liquid phase epitaxial process
The film layer of PBAs；
S4, step S3 is repeated, obtains being grown in the PBAs film in nickel foam；
S5, high-temperature calcination obtain electro-catalysis and produce oxygen thin-film electrode material.
8. preparation method according to claim 1-7, which is characterized in that prepare PBAs film in nickel foam
Method is for example including following steps: the solution of the solution of cobalt acetate and the potassium ferricyanide successively being impregnated nickel foam, in nickel foam
Form PBA (Co-Fe) film: PBA (Co-Fe)/NF；
Preferably, the successively immersion sequence are as follows: cobalt acetate solution → distilled water → potassium ferricyanide solution → distilled water.
9. the electro-catalysis as prepared by claim 1-8 described in any item methods produces oxygen thin-film electrode material, which includes
Nickel foam and the metal-oxide film being attached in nickel foam.
10. the application that electro-catalysis as claimed in claim 9 produces oxygen thin-film electrode material, which is characterized in that the material is as work
Make electrode, preferably as the anode working electrode of electrolysis water, for OER catalysis reaction.
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